Process for the production of a chalcopyrite structure semiconductor thin film containing a specific dopant

Abstract: Methods to produce a I-III-VI 2 chalcopyrite semiconductor film containing a Group VII element as a dopant are provided. The chalcopyrite film produced according to the process of the present invention has stoichiometric composition, and electrical characteristics such as p-n conduction type, carrier concentration and the like are controlled.

Description: BACKGROUND OF THE INVENTION Field of the invention The present invention relates to a process for the production of a chalcopyrite structure semiconductor thin film containing a specific dopant. Description of the Related Art The chalcopyrite structure semiconductor is a material useful for constituting light-emitting devices and solar cells, because its forbidden band can be wide from a visual region to an infrared ray region and it has a large optical absorption coefficient due to the constituent elements. It is indispensable to produce a p-n junction in manufacturing the solar cells or light-emitting devices. For controlling a p-n conduction type of the chalcopyrite thin film, a method of changing the composition ratio between a Group I element and a Group III element or between a Group II element and a Group IV element which are the constituent elements of chalcopyrite compounds has been used conventionally. For example, in the case of CuInSe 2 thin film, the n-type is formed when the proportion of the Group I element Cu is less than that of the Group III element In, and in the opposite case the p-type is formed. In these cases, a problem is encountered in that many lattice defects occur due to deviations in the composition ratio. There are also such problems as depositions of excessive amounts of components or the appearance of an impurity phase other than the chalcopyrite structure. R. Noufi et al. also report that it is difficult to control the carrier concentration and resistivity by changing the composition ratio (Appl. Phys. Lett., 45 (1984) p.688). Particularly, most of the chalcopyrite semiconductor thin films which go in the direction of the n-type by deviation in the composition ratio show a high resistance, and thus a low resistance film is not obtainable. In fabricating the p-n junction by using the chalcopyrite thin film produced by the prior art, such inconvenience as the lattice defects and depositions of excessive amounts of components owing to deviations of composition ratio, or the impurity phase other than the chalcopyrite structure appear as mentioned before. Thereby, electrical and optical characteristics of the chalcopyrite thin film are deteriorated. Thus, when the devices having the p-n junction are manufactured by using the chalcopyrite thin film produced by the prior art, efficiency of the devices are inferior due to the deterioration of electrical and optical characteristics. For example, by increase of carrier recoupling centers due to the lattice defects and the impurity phase, the open-circuit voltage of the solar cell drops and also the quantum efficiency of semiconductor laser drops. When an n-type high resistance film is used, in the solar cells the short-circuit current decreases, and in the light-emitting devices the carrier injection efficiency reduces. Thus, the conversion efficiency of the solar cells and the luminous efficiency of the light-emitting devices are deteriorated. Moreover, in the solar cells, the depletion layer of the p-n junction must be broadened to convert incident light efficiently into electrical energy. Thus, it is necesary to control the carrier concentration. The US-A-4004342 concerns a method of manufacturing light emitters and photovoltaic detectors by implanting bromine or chlorine ions into a p-type CuInSe 2 substrate so as to form a p-n junction. SUMMARY OF THE INVENTION The present invention provides a process of producing a chalcopyrite structure semiconductor film comprising a Group I-III-VI 2 chalcopyrite compound containing a Group VII element as a dopant. The present invention further relates to a process of producing a chalcopyrite thin film, whereby conventional problems are solved, constituent element composition is in a stoichiometric ratio and electrical characteristics such as p-n conduction types and carrier concentration are controlled. A first process of producing the chalcopyrite structure semiconductor film of the present invention comprises the steps of: depositing a I-III-VI 2 chalcopyrite compound film on a substrate, and heat treating the deposited chalcopyrite compound film in an atmosphere containing a vapor of a Group VII element or of a compound thereof to obtain a I-III-VI 2 chalcopyrite compound film containing the Group VII element therein as a dopant. In a preferred embodiment, the process further comprises the step of heat treating the chalcopyrite compound film containing the Group VII element as a dopant, preferably in an atmosphere containing gas selected from the group consisting of hydrogen, nitrogen, oxygen, helium and argon. The preferable temperature of the heat treating lies in the range of from 200°C to 400°C. In another preferred embodiment, the process further comprises the step of heat treating the chalcopyrite compound film containing the Group VII element as a dopant in an atmosphere containing a vapor of the Group VI element. In still another embodiment, the heat treating the deposited chalcopyrite compound film in the atmosphere containing the vapor of the Group VII element or its compound is carried out under a vacuum of 1.33 · 10 -7 Pa to 1.33 Pa (10 -9 Torr to 10 -2 Torr). A second process of producing the chalcopyrite structure semiconductor film of the present invention comprises the steps of: depositing a I-III-VI 2 chalcopyrite compound film on a substrate, and heat treating the deposited chalcopyrite compound film in an atmosphere containing a gaseous compound of a Group VII element to obtain a chalcopyrite compound film containing the Group VII element therein as a dopant. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a longitudinal sectional view showing a schematic configuration of an apparatus for obtaining a I-III-VI 2 chalcopyrite structure semiconductor thin film doped with a Group VII element according to one embodiment of the present invention. Fig. 2 shows the relationship between a substrate temperature, an InCl 3 crucible temperature at the time of heat treating a CIS film and resistivity of a resultant CIS:Cl film in embodiment 1 of the present invention. Fig. 3 shows the relationship between a HCl content in an atmosphere, a heat treatment temperature at the time of heat treating a CIS film and resistivity of a resultant CIS:Cl film in embodiment 2 of the present invention. Fig. 4 shows as curves "b" and "c" distributions of Cl element in a CIS:Cl film obtained in embodiments 1 and 2 as mentioned above. DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a method for the production of a Group I-III-VI 2 chalcopyrite structure semiconductor film containing a Group VII element as a dopant. In the I-III-VI 2 chalcopyrite structure semiconductor thin film produced according to the process of the present invention and containing the Group VII element as a dopant, the composition of constituent elements is in a stoichiometric ratio, and electrical characteristics such as p-n conduction types and carrier concentration are controlled. According to the first or second production process of the present invention, by heat treating the deposited I-III-VI 2 thin film in an atmosphere containing a vapor of the Group VII element or its compound, or an atmosphere containing a gaseous compound of the Group VII element under a vacuum or a gas atmosphere, the Group VI element in the I-III-VI 2 chalcopyrite is substituted by the Group VII element (hereinafter, these production processes are referred to as "diffusion process"). As mentioned above, the I-III-VI 2 chalcopyrite structure semiconductor thin film obtained by the present invention becomes a semiconductor film showing an n-type conduction in the presence of excessive electrons caused by partial substitution of the Group VI element by the Group VII element. The ratio of the element (dopant) substituted partly as aforementioned against the main element is very small, usually 0.1 atomic % or less, and therefore, the composition ratio of the resultant chalcopyrite thin film can be kept in a stoichiometric ratio. Thus, there is no appearance of lattice defects and excessive component depositions due to the deviation of the composition ratio nor appearance of an impurity phase other than the chalcopyrite structure. Also, in such a production process, by controlling the evaporating velocity of the Group VII element as the dopant or its compound, or a flow rate of gaseous compound or the Group VII element, the carrier concentration or resistivity of the resultant film can be controlled. Thus, the degree of freedom on designing the solar cells or light-emitting devices increases, and the desired carrier concentrations or the like necessary for the devices can be obtained easily. Since the substitution takes place from the surface of the chalcopyrite thin film when substituting the dopant and the main element by using the diffusion process, the Group VII element tends to concentrate near the surface, and the concentration inside the film becomes gradually thinner as the depth increases. When such a distribution has occurred, for example, in the solar cells, an internal electric field is produced in the n-type semiconductor film, and minority carriers (in this case, positive holes) produced near the surface are accelerated inwardly or to the p-n junction interface from the film surface. Therefore, the carrier recouplings in the n-type film decrease and a large amount of electric current can be obtained. Moreover, by the heat treatment of the n-type chalcopyrite thin film obtained by the aforementioned process, the activation factor of the dopant being substituted (the amount of applied electron against the amount of dopant being substituted) can be improved. That is, a low resistance n-type film can be obtained with a little amount of dopant, and the deterioration of crystalline quality such as the disturbance of the chalcopyrite structure due to excessive impurities is eliminated. Moreover, the n-type chalcopyrite film as formed by the diffusion process can be used in a process of optimizing the efficiency of devices such as the solar cells, because the distribution form of the dopant can be controlled by the heat treatment temperature and time. Since the n-type chalcopyrite thin film obtained by the aforementioned process has little lattice defects and deposition of excessive components or an impurity phase, the carrier recoupling center decreases, and therefore based on it one can realize solar cells having a high conversion efficiency and also light-emitting devices having a high luminous efficiency. The range of an appropriate temperature for the heat treatment in the second process of the invention in order to produce the chalcopyrite structure semiconductor film is between 300°C and 600°C. Although the temperature of heat treatment for the chalcopyrite structure films may differ depending on their constituent elements, a film of high quality is not expected to be obtained by means of a heat treatment at a temperature lower than 300°C. And when the heat treatment is made at a temperature higher than 600°C, the film composition changes due to desorption of a Group VI element, or Group III and VI elements from the film. The Group I element which is applicable to the process of the present invention is, for instance, Cu or Ag. The Group III element which is applicable to the process of the present invention is, for instance, Al, Ga or In. The Group VI element which is applicable to the process of the present invention is, for instance, S, Se or Te. Further, as the gaseous compound of the Group VI element which is applicable to the present invention, for instance, H 2 S, CS 2 , H 2 Se, (CH 3 ) 2 Se, (C 2 H 5 ) 2 Se or the like may be exemplified. The Group VII element which is applicable to the process of the present invention is, for instance, F, Cl or Br. Further, as the gaseous compound of the Group VII element, for instance, HCl, HF or the like may be exemplified. In the following, the embodiments of the present invention are described with reference to the drawings. Embodiment 1 Fig. 1 shows a schematic configuration of an apparatus for obtaining a chalcopyrite structure semiconductor thin film. In a vacuum container 1, a support 4 is disposed holding a substrate 2 for depositing a chalcopyrite thin film thereon and including heater 3 for heating the substrate 2. Moreover, in the container 1, a source 5 of Cu, a source 6 of In and a source 7 of Se, which are main constituent elements of chalcopyrite compound CuInSe 2 , and a source 8 of a dopant including InCl 3 are provided. An opening 9 is connected to an exhaust system. Description will be made on an example of the production process, whereby the group VI element in the film is substituted by the Group VII element, by heating the film while evaporating the group VII element thereabout after depositing a I-III-VI 2 chalcopyrite thin film. Hereinafter, this process is referred to as "vapor-phase diffusion process". Using the above-described vacuum container as shown in Fig.1, Cu, In and Se are heated to respective temperatures of 1140°C, 860°C and 200°C in order to produce a CIS film at the substrate temperature of 500°C. Then, the substrate temperature is maintained within a temperature range of 200 to 400°C, while evaporating InCl 3 from the source in vacuum about 1.33 · 10 -5 Pa to heat the CIS film. Fig. 2 shows the relationship between the substrate temperature, the InCl 3 crucible temperature and the resistivity of the heat treated film. Hereupon, the heat treatment time is fixed at 30 minutes. The compositions of all of the heat treated films substantially satisfy the stoichiometric composition ratio, and show the n-type conduction. When the substrate temperature is 200°C, the change of the film resistivity is small against the changes in the InCl 3 crucible temperatures, and at an InCl 3 crucible temperature of 150°C it is not so much different from the resistivity of about 10 4 Ωcm of the CIS film without Cl. When the substrate temperature is adjusted to 300°C, the resistivity drops abruptly as the InCl 3 crucible temperature rises, and at an InCl 3 crucible temperature of 300°C, the resistivity drops to about 10Ωcm. This value is lower by three digits than the resistivitiy of the CIS film without Cl. On the base of this fact it is understood that the resistivity can be controlled by means of the InCl 3 crucible temperature. The temperature range of the substrate for rendering favorable results is 300°C to 500°C. Embodiment 2 Description will be made on an example of the production process, whereby the group VI element in the film is substituted by the group VII element, by heating the I-III-VI 2 chalcopyrite thin film in a gaseous atmosphere containing the group VII element after being deposited on the substrate. Hereinafter, this process is referred to as "gas heat treatment process". The CIS film produced at a substrate temperature of 500°C by the same process as the aforementioned embodiment 1 was fed into a quartz tube and then heated while mixed gas of HCl and N 2 was being introduced to the quartz tube. The flow rate of the mixed gas was 200ml/min. and the heat treatment time was one hour. Fig. 3 shows the relationship between the HCl gas content in the mixed gas, the heat treatment temperature and the resistivity of the heat treated CIS film. Hereupon, all of the resultant films were of the n-type. Regardless of the HCl content, the film resistivity drops as the heat treatment temperature rises. Particularly, when the HCl content is 10 vol.% and the heat treatment temperature is 400°C, the film resistivitiy drops to about 10 -2 Ωcm. This value is lower than the resistivity before the heat treatment by about 6 digits. However, the film surface heated at an HCl content of 10 vol.% at 350°C or higher was irregular and rough. Therefore, it is believed that by using the mixed gas having a high HCl content at a high heat treatment temperature, the film surface is etched by or reacted with HCl. On the base of X-ray diffraction, it is understood that the crystalline quality evaluated by means of the half width of a 112 diffraction peak of the chalcopyrite structure CIS film is considerably worse as compared with the film before the heat treatment. On the contrary, in the case of the heat treatment using gas having a HCl content of 5 vol.% or less, the same roughness of the film surface and the deterioration of crystalline quality were not observed regardless of the heat treatment temperature. It is understood from the figure that, when comparing the HCl contents of 5 vol.% and 1 vol.%, the resistivity drops at respective heat treatment temperature as the HCl content increases. Thereby it is understood, that the film resistivity can be controlled by means of the heat treatment temperature and the HCl content in the mixed gas. Though the above-mentioned embodiment shows the case of using N 2 as dilution gas of HCl, the same results were obtained by using H 2 , He and Ar. Fig. 4 shows results of testing distributions of Cl elements in the CIS:Cl film produced in the aforementioned embodiments 1 and 2 by a secondary ion mass analysis. The curve "b" shows that as obtained by the vapor-phase diffusion process. The curve "c" shows that as obtained by the gas heat treatment process. The curve "d" is to be described later. The results shown are tested (i) on the films heated at the substrate temperature of 300°C and the InCl 3 crucible temperature of 250°C for 30 minutes for the vapor-phase diffusion process, and (ii) on the film as heated at 300°C in mixed gas having the HCl content of 5 vol.% for the gas heat treatment process. It is understood that, in the vapor-phase diffusion process and gas heat treatment process, Cl is distributed mostly near the film surface, whereas its content decreases as approaching the substrate. When comparing the Cl distribution in the film as obtained by means of vapor-phase diffusion process and the gas heat treatment process, it is smaller in the latter case. Thereby, the production process to be adopted can be selected by means of the configuration or design of the devices to be produced. Embodiment 3 Description will be made on the result of heating the CIS:Cl film produced by the vapor-phase diffusion process in an Ar atmosphere at 400°C for 30 minutes. Hereinafter, this is referred to as "after heat treatment". As regards the film produced by the vapor-phase diffusion process, the resistivity of the film heated at the substrate temperature of 200°C increased due to the after heat treatment, and the resistivity of the film heated at 300°C or higher decreased by about one digit. This is considered as being based on the fact, that in the film heated at a substrate temperature of 200°C, Cl near the film surface has been diffused in the film and is diluted by means of the after heat treatment. On the contrary, it is believed that in the film produced at a substrate temperature of 300°C or higher, though Cl near the film surface diffuses by the after heat treatment, the activation factor increases furthermore. The curve "d" in Fig. 4 shows the Cl distribution of the film obtained by means of the vapor-phase diffusion process and heated at the substrate temperature of 300°C and InCl 3 crucible temperature of 250°C for 30 minutes, after the heat treatment in the Ar atmosphere at 400°C for 30 minutes. It is understood that Cl is distributed equally in the film as compared with the film which is not subjected to the after heat treatment and shown by the broken line. Although the chalcopyrite compound film is deposited by means of a three-source evaporation in the above-mentioned embodiments, another preferable deposition method, for example the sputtering or selenization of Cu/In layers in an H 2 Se atmosphere may be employed in the present invention. Additionally, the following is a brief explanation for the phrase "after heat treatment". The appropriate temperature for said heat treatment is between 200°C and 600°C. The heat treating time even at the lowest temperature is shorter than 5 hours. As the temperature increases, the treating time becomes shorter. As stated above, such an after heat treatment will render an activation of the dopant or a controlled distribution of the dopant.

Claims: A process of producing a chalcopyrite semiconductor film comprising the steps of: depositing a Group I-III-VI 2 chalcopyrite compound film on a substrate, and heat treating said chalcopyrite compound film in an atmosphere containing a vapor of a Group VII element or of a compound thereof to obtain a I-III-VI 2 chalcopyrite compound film containing said Group VII element as a dopant. The process in accordance with claim 1 wherein said heat treating is carried out under a vacuum of 1.33 · 10 -7 Pa to 1.33 Pa (10 -9 Torr to 10 -2 Torr). The process in accordance with claim 1 which further comprises the second step of heat treating said chalcopyrite compound film. The process in accordance with claim 3 wherein said second step of heat treating is carried out in an atmosphere containing at least one member selected from the group consisting hydrogen, nitrogen, oxygen, helium and argon. The process in accordance with claim 3 wherein said second step of heat treating is carried out in an atmosphere containing a vapor of the Group VI element. A process of producing a chalcopyrite semiconductor film comprising the steps of: depositing a Group I-III-VI 2 chalcopyrite compound film on a substrate, and heat treating the deposited chalcopyrite compound film in an atmosphere containing a gaseous compound of a Group VII element to obtain a chalcopyrite compound film containing said Group VII element therein as a dopant.

Inventors: KOHIKI SHIGEMI, NEGAMI TAKAYUKI, NISHITANI MIKIHIKO, WADA TAKAHIRO, KOHIKI, SHIGEMI, NEGAMI, TAKAYUKI, NISHITANI, MIKIHIKO, WADA, TAKAHIRO
Applicants: MATSUSHITA ELECTRIC IND CO LTD, MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD.
Application year: 1994
Main classification: H01L31
IPC codes: H01L31